Prepn process of 2,3,3',4'-diphenyl tetraformic dianhydride and its derivative

A technology of biphenyltetracarboxylic dianhydride and phthalic acid diester is applied in 2 fields, can solve problems such as low yield, and achieve the effects of high yield and simple separation method

Inactive Publication Date: 2003-08-20
CHANGCHUN INST OF APPLIED CHEMISTRY - CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The 2,3,3',4'-biphenyltetracarboxylic dianhydride involved in the reported patents is a by-produc

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0016] Under the protection of nitrogen, 0.5mol dimethyl 4-chlorophthalate, 0.5mol dimethyl 3-chlorophthalate, 0.025mol nickel dichloride, 0.15mol triphenylphosphine, 0.1mol Add sodium bromide and 400ml of DMAc solvent into a 500ml three-necked flask, wait until the temperature rises to 80°C, add 1.5mol of zinc powder after stirring, the solution turns reddish brown, and the reaction can be completed after 2 hours. Pour the reaction solution into water, filter to collect the precipitate, then add it to NaOH aqueous solution, heat for 4 hours, filter after cooling, acidify the filtrate to strong acidity with concentrated hydrochloric acid, filter out the precipitated solid, add toluene to the filtrate and heat Reflux with water, when the water in the system is completely removed, filter it while it is hot, and precipitate the solid. After the solid is fully dried, sublimate at 210°C to obtain 2,3,3',4'-biphenyltetracarboxylic dianhydride 0.5mol.

Embodiment 2

[0018] Under the protection of nitrogen, 0.3mol 4-chlorophthalic acid diethyl ester, 0.7mol 3-chlorophthalic acid diethyl ester, 0.04mol nickel dibromide, 0.24mol trimethylphosphine, 300ml Add DMSO solvent into a 500ml three-neck flask, wait for the temperature to rise to 60°C, stir for ten minutes, then add 1.5mol zinc powder, the solution turns reddish brown, and the reaction can be completed after 0.5h. The yield of tetraethyl 2,3,3',4'-biphenyltetracarboxylate was 47.4% as measured by liquid chromatography.

Embodiment 3

[0020] Under the protection of nitrogen, 0.3mol 4-di-n-propyl chlorophthalate, 0.7mol 3-di-n-propyl chlorophthalate, 0.125mol nickel dibromide, 0.15mol trimethylphosphine, Add 300ml of DMAc solvent into a 500ml three-neck flask, wait for the temperature to rise to 68°C, stir for ten minutes, then add 1.1mol of zinc powder, the solution turns reddish brown, and the reaction can be completed after 4 hours. The yield of tetra-n-propyl 2,3,3',4'-biphenyltetracarboxylate as measured by liquid chromatography was 70%.

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Abstract

The present invention is the preparation process of 2,3,3',4'-diphenyl tetraformic dianhydride and its derivative. Through the coupling reaction in non-proton polar solvent with 3- and 4- chloro o-dippthalate or 3- and 4-chlorophthalimide as basic material, nickel halide as catalyst, trialkylphosphine as ligand and zinc powder as reductant, diphenyl tetraformate or diphenyl tetraformyl diimide is prepared. The produced diphenyl tetraformate or diphenyl tetraformyl diimide is then hydrolyzed in NaOH solution and concentrated HCl acidified to obtain 2,3,3',4'-diphenyl tetraformic acid, which is further reflux treated in toluene or xylene or vacuum high-temperature sublimed to obtain 2,3,3',4'-diphenyl dianhydride.

Description

technical field [0001] The invention belongs to the preparation method of 2,3,3',4'-biphenyltetracarboxylic dianhydride and derivatives thereof. Background technique [0002] The synthesis and application of biphenyltetracarboxylic dianhydride and its derivatives as important monomers of high-performance aromatic polyimides have already received widespread attention at home and abroad. Wherein 3,3',4,4'-biphenyltetracarboxylic acid and its derivatives have many patent reports (U.S. Patent: 5081281; Japanese Patent 7352749,80141417,8551151,8020705). Including the dehalogenation coupling reaction of halogenated tetraalkyl phthalate and the oxidative coupling reaction of tetraalkyl phthalate. The 2,3,3',4'-biphenyltetracarboxylic dianhydride involved in the reported patents is a by-product of the synthesis of 3,3',4,4',-biphenyltetracarboxylic dianhydride , and the yield is very low. Contents of the invention [0003] The purpose of this invention is to provide a kind of 2...

Claims

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Application Information

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IPC IPC(8): C07D407/10
Inventor 王震吴雪娥高昌录丁孟贤高连勋
Owner CHANGCHUN INST OF APPLIED CHEMISTRY - CHINESE ACAD OF SCI
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